Facile one-pot synthesis of chromeno[4,3-b] quinoline derivatives catalyzed by Cu(II)-Schiff base/SBA-15

Article abstract of DOI:10.1515/hc-2014-0024

A novel, one-pot, simple, environmentally benign and efficient protocol has been employed for the synthesis of chromeno[4,3-b]quinoline derivatives in the presence of catalytic amounts of Cu(II)-Schiff base/SBA-15 under solvent-free conditions in excellen

Full text of DOI:10.1515/hc-2014-0024

Heterocycl. Commun. 2014; 20(3): 181–184
Radineh Motamedi*, Ghasem Rezanejade Bardajee and Somaye Shakeri
Facile one-pot synthesis of chromeno[4,3-b]
quinoline derivatives catalyzed by Cu(II)-Schiff
base/SBA-15
Abstract: A novel, one-pot, simple, environmentally efforts to improve conditions for the Hantzsch reaction
benign and efficient protocol has been employed for the [15–19], in particular by using silica gel-supported cata-
synthesis of chromeno[4,3-b]quinoline derivatives in the lysts [20–28].
presence of catalytic amounts of Cu(II)-Schiff base/SBA-15
There are a few literature reports regarding the appli-
under solvent-free conditions in excellent yields and rates. cation of silica supported Schiff base cobalt(II) (Co/
SBA-15) and copper(II) (Cu/SBA-15) complexes as catalysts
Keywords: chromeno[4,3-b]quinoline; heterogeneous in organic synthesis [29–34].
catalyst; SBA-15.
Herein, we describe a one-pot, simple, new, and effi-
cient protocol for the synthesis of chromeno[4,3-b]qui-
nolines, using the catalytic Cu(II)-Schiff base/SBA-15. To
the best of our knowledge, there is no report on the use
of this type of catalyst in the synthesis of 1,4-DHPs. The
catalyst is prepared by anchoring the copper complex to
mesoporous silica SBA-15 [33, 34] (Figure 1).
DOI 10.1515/hc-2014-0024
Received December 3, 2013; accepted March 19, 2014
Introduction
The synthetic pathway to the products 5a–k by the
reaction of 1,3-cyclohexanedione (1), a benzaldehyde 2,
and 4-aminocoumarin (4) is outlined in Table 1. The reac-
tion with 4-nitrobenzaldehyde was chosen as a model
for optimization. In the first step, substrates 1 and 2 were
allowed to undergo Knoevenagel condensation under sol-
vent-free conditions at 100°C for 10 min to yield the inter-
mediate product 3. This reaction was monitored by TLC
analysis.
For the subsequent Michael addition, the intermedi-
ate product 3, without isolation, was treated with 4-ami-
nocoumarin (4) and the catalyst. This second step was
conducted at 200°C for 5 min, at which time the interme-
diate Michael adduct underwent intramolecular cycliza-
tion to the desired product 5b. It should be noted that this
second step requires heating for 1 h to 200°C in the absence
of the catalyst [11]. The yield of 5b is low for the reaction
conducted in the absence of the catalyst. To analyze the
scope and limitations of this procedure, a number of prod-
ucts 5 were obtained by using the optimized conditions
(Table 1). All products were obtained quickly and in high
yields in the presence of the catalyst.
1,4-Dihydropyridines (1,4-DHPs), particularly 4-aryl-sub-
stituted 1,4-dihydropridines, are well known as calcium
channel modulators and have emerged as one of the
most important class of drugs for the treatment of car-
diovascular disease [1, 2]. They also possess a variety of
other biological activities [3]. 1,4-DHPs can be obtained
by classical Hantzsch method, which involves cyclocon-
densation of an aldehyde, a 1,3-diketone or β-ketoester
and an amine either in acetic acid or in ethanol under
reflux [4]. Recently, several modifications to this clas-
sical method have been reported, including the use of
catalysts such as Bronsted acid [5], lithium iodide [6],
scandium triflate [7], cerium ammonium nitrate [8],
magnesium perchlorate [9], and copper(II) oxide [10].
We have recently synthesized a new class of coumarin-
fused dihydropyridines 5a–k (Table 1) in moderate yields
under solvent-free conditions [11–14]. In this paper, we
report a greatly improved synthesis of compounds 5a–k
in the presence of a catalyst Cu(II)-Schiff base/SBA-15
(structure in Figure 1). This work is part of our research
*Corresponding author: Radineh Motamedi, Department of
Chemistry, Payame Noor University, PO Box 19395 3697, Tehran,
Iran, e-mail: r_motamedi@pnu.ac.ir
Ghasem Rezanejade Bardajee and Somaye Shakeri: Department
of Chemistry, Payame Noor University, PO Box 19395 3697, Tehran,
Iran
The reusability of the Cu(II)/SBA-15 catalyst was inves-
tigated. After the first catalytic cycle, the catalyst was
removed from the mixture by filtration and successfully
used in 10 subsequent runs, without any significant loss
in catalytic activity. No pretreatment step was required,
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182ꢀ ꢀR. Motamedi et al.: Synthesis of chromeno[4,3-b]quinoline derivatives
Table 1ꢂSynthesis of 7-aryl-8,9,10,12-tetrahydro-7H-chromeno[4,3-b]quinoline-6,8-diones 5a–k catalyzed by Cu(II)-Schiff base/SBA-15.
10
NH2
11
9
11a
8
12
CHO
HN
O
7a
7
1
4
O
O
12a
14
O
O
1a
13
15
4
2
3
CH
6a
R
16
O
O18 17
Cu(II)-Schiff
base/SBA-15
4a
6
O
O
R
5
1
2
R
3
5a-k
Compoundꢁ
R
ꢁ
mpaꢁ
Yieldb,c (%)
5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
2-nitro
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢀ> ꢀ300 (ꢀ> ꢀ300)ꢃ
260 (260–262)ꢃ
ꢀ> ꢀ310 (ꢀ> ꢀ310)ꢃ
207 (208–210)ꢃ
214 (214–216)ꢃ
265 (267–269)ꢃ
295 (294–296)ꢃ
190 (188–190)ꢃ
ꢀ> ꢀ310 (310)ꢃ
75 (35)
70 (45)
90 (50)
93 (50)
74 (55)
71 (60)
77 (65)
86 (45)
78 (74)
89 (75)
80 (75)
4-nitro
2-chloro
3-chloro
4-chloro
3-bromo
4-bromo
2-methyl
3-methyl
2-methoxyꢃ
4-methoxyꢃ
ꢀ> ꢀ310 (ꢀ> ꢀ310)ꢃ
275 (276–278)ꢃ
aThe numbers in parentheses refer to melting points in the literature [11].
bIsolated yields of pure compounds.
cThe numbers in parentheses refer to yields in the literature [11].
O
O
Experimental
Cu
N
N
Preparation of the catalyst Cu(II)-Schiff
base/SBA-15
Si
Si
O
O
O
O
O
O
The Cu(II)-Schiff base complex was prepared using the literature pro-
cedure [33] with the following modification. Activated silica gel SBA-
15 (1.5 g) was suspended in a methanol solution of the Schiff base
complex, and the mixture was stirred at room temperature for 24 h.
The solvent was removed using a rotary evaporator, and the result-
ing green solid was dried at 80°C overnight. The final product was
washed with MeOH and deionized water until the washings were
colorless to ensure that the noncovalently grafed complex and phys-
ically adsorbed metal species were removed. Further drying was car-
ried out in an oven at 80°C for 8 h. To measure the amount of copper
loaded into SBA-15, the catalyst (0.1 g) was digested with HNO3 by stir-
ring at room temperature for a week. Then the mixture was filtered,
and the total amount of copper in SBA-15 in the colorless sample was
determined as 0.14 mmol/g by atomic absorption spectroscopy.
Figure 1ꢂStructure of catalyst Cu(II)-Schiff base/SBA-15.
although the recovered catalyst was washed with 5 mL of
MeOH to remove traces of the previous reaction mixture
and dried before the next cycle.
The mechanism for the formation of 5a–k in the
absence of catalyst has been suggested [11]. Coordination
of the carbonyl groups in the intermediate products by the
Cu2+ cation of the catalyst may increase electrophilicity of
the carbonyl derivatives in both the Knoevenagel conden-
sation and the Michael addition step.
In summary, a one-pot, convenient, environmentally
benign, and safe synthetic method for chromeno[4,3-b]
quinoline was developed. The simplicity of the method,
including mild reaction conditions and the ease of product
isolation, will make it attractive for use on an industrial
scale. Most important, the purification procedure only
involves filtration, washing, and drying.
General procedure for synthesis of
chromeno[4,3-b]quinoline-6,8-diones 5a–k
A mixture of an aromatic aldehyde (1, 1.0 mmol) and 1,3-cyclohex-
adione (2, 1.0 mmol) were thoroughly mixed in a beaker using a
spatula. Then the beaker was placed in an autoclave at 100°C for
10 min to complete the condensation reaction to 3, as monitored by
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ꢂ183
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